Enhancement of Negative Photochromic Properties of Naphthalene‐Bridged Phenoxyl‐Imidazolyl Radical Complex

Abstract Negative photochromism has increased attention as a light‐switch for functional materials. A development of fast photochromic molecules has been also expected because a rapid thermal back reaction within a millisecond time scale is useful for real‐time switching. Herein, we synthesized the derivatives of the naphthalene‐bridged phenoxyl‐imidazolyl radical complex (Np−PIC) showing the negative photochromism to demonstrate the efficient strategy to increase the visible light sensitivity and to control the thermal back reaction rates. The distances of the C−C bond of the transient 2,4’‐isomer shows good agreement with the thermodynamic stability, leading to the control of the thermal back reaction rate. We revealed the cyclic voltammetry and the DFT calculations are efficient to predict the characters of the HOMO and LUMO. The introduction of the electron‐withdrawing dicyanoquinodimethane group is efficient to induce the photochromic reaction with increased visible‐light sensitivity by the expansion of the π‐conjugation. The results will give an important insight for the future development of fast‐responsive negative photochromic molecules.